The present invention relates to a process for preparing a vinylpyrrolidone polymer, wherein a specific redox initiator is employed. Particularly, the present invention relates to a process for preparing a vinylpyrrolidone polymer which is not colored, does not give off a bad smell, and contains extremely little impurities (for example, remaining monomers or by-products).
One of the conventional processes for polymerization of vinylpyrrolidone is a process using aqueous hydrogen peroxide as an initiator (DE-B922378). However, when the process is employed, pH control is required during the polymerization. The process also has problems that 2-pyrrolidone is produced as a by-product in proportion to the amount of hydrogen peroxide (Polymer Journal, vol. 17, No. 1, pp143-152 (1985)), or that products are colored. The above process is effective for preparing a vinylpyrrolidone polymer having a low molecular weight, but because products are colored, another process has been expected especially for a cosmetic use.
The process using azo compounds as an initiator is disclosed (Japanese Unexamined Patent Publication No. 38403/1989). Even by the process, impurities derived from the initiator remain in products, and therefore the process is not useful for a cosmetic use.
The process using a redox initiator consisting of a peroxide and Rongalit is disclosed (Japanese Unexamined Patent Publication No. 215302/1984). It is predicted in the process that a bad smell will be caused because aldehyde remains as an impurity in products. Therefore, the process seems inappropriate for a cosmetic use.
The process using di-tert-butyl peroxide singly as an initiator is also disclosed (Japanese Examined Patent Publication No. 19174/1996). However, polymerization requires to be carried out at 100xc2x0 C. or more under a pressurized condition because the decomposition temperature of di-tert-butyl peroxidede is high.
It is an object of the present invention to provide a vinylpyrrolidone polymer which is little colored, gives off a bad smell little, and contains extremely little impurities.
The present invention relates to a process for preparing a vinylpyrrolidone polymer, wherein a water-soluble organic peroxide and a sulfite are added to a vinylpyrrolidone aqueous solution to polymerize vinylpyrrolidone, and to obtain a vinylpyrrolide polymer.
The present invention relates to the above-mentioned process for preparing a vinylpyrrolidone polymer, wherein a K value of the resulting vinylpyrrolidone polymer evaluated according to Fikentscher method is 10 to 120.
The present invention relates to each of the above-mentioned processes for preparing a vinylpyrrolidone polymer, wherein the water-soluble organic peroxide is added in an amount of 0.005 to 5% by weight and the sulfite is added in an amount of 0.005 to 10% by weight based on the vinylpyrrolidone.
The present invention relates to each of the above-mentioned processes for preparing a vinylpyrrolidone polymer, wherein the mole ratio of the water-soluble organic peroxide and the sulfite is 1:0.5 to 1:20.
The present invention relates to each of the above-mentioned processes for preparing a vinylpyrrolidone polymer, wherein the water-soluble organic peroxide and the sulfite are added to the reaction solution in installments for the polymerization.
The present invention relates to each of the above-mentioned processes for preparing a vinylpyrrolidone polymer, wherein the amount of the sulfite added initially is determined so that the mole ratio of the vinylpyrrolidone and the amount of the sulfite added initially is 1:0.0004 to 1:0.1.
The present invention relates to each of the above-mentioned processes for preparing a vinylpyrrolidone polymer, wherein the polymerization temperature of vinylpyrrolidone is 10 to 90xc2x0 C.
The present invention relates to each of the above-mentioned processes for preparing a vinylpyrrolidone polymer, wherein the sulfite is ammonium sulfite.
The present invention relates to each of the above-mentioned processes for preparing a vinylpyrrolidone polymer, wherein the water-soluble organic peroxide is a hydroperoxide.
The present invention relates to each of the above-mentioned processes for preparing a vinylpyrrolidone polymer, wherein the water-soluble organic peroxide is tert-butyl hydroperoxide.
The present invention relates to each of the above-mentioned processes for preparing a vinylpyrrolidone polymer, wherein at most 10 ppm of vinylpyrrolidone is contained in the resulting vinylpyrrolidone polymer.
The present invention relates to a vinylpyrrolidone polymer containing a little amounts of vinylpyrrolidone, which is obtained by adding a water-soluble organic peroxide and a sulfite to a vinylpyrrolidone aqueous solution to polymerize vinylpyrrolidone.
The present invention relates to the above-mentioned vinylpyrrolidone polymer which contains at most 10 ppm of vinylpyrrolidone based on the vinylpyrrolidone polymer.
The present invention relates to a vinylpyrrolidone polymer, which has a K value evaluated according to Fikentscher method of 10 to 40, and Hazen No. (APHA) value in a 10% aqueous solution according to JIS K3331 of at most 10, and which contains at most 10 ppm of remaining vinylpyrrolidone based on the vinylpyrrolidone polymer.
In the process for preparing a vinylpyrrolidone polymer of the present invention, a vinylpyrrolidone polymer is prepared by adding a water-soluble organic peroxide and a sulfite as a redox initiator to a vinylpyrrolidone (hereinafter referred to as xe2x80x9cVPxe2x80x9d) aqueous solution to initiate the polymerization.
Vinylpyrrolidone (VP) ordinarily means N-vinyl-2-pyrrolidone. A vinylpyrrolidone polymer implies a VP homopolymer and a copolymer consisting of VP and other monomers (the copolymer contains preferably at least 20% by weight, more preferably at least 30% by weight of VP units).
As other monomers, for example, acrylic acid, methacrylic acid, an alkylester of acrylic acid (for example, methyl acrylate and ethyl acrylate), an alkylester of methacrylic acid (for example, methyl methacrylate and ethyl methacrylate), an aminoalkylester of acrylic acid (for example, diethylaminoethyl acrylate), an aminoalkylester of methacrylic acid, a monoester of acrylic acid and a glycol, a monoester of methacrylic acid and a glycol (for example, hydroxyethyl methacrylate), an alkaline metal salt of acrylic acid, an alkaline metal salt of methacrylic acid, ammonium salt of acrylic acid, ammonium salt of methacrylic acid, a quaternary ammonium derivative of an aminoalkylester of acrylic acid, a quaternary ammonium derivative of an aminoalkylester of methacrylic acid, a quaternary ammonium compound of diethylaminoethylacrylate and methyl sulfate, vinyl methyl ether, vinyl ethyl ether, an alkaline metal salt of vinyl sulfonic acid, ammonium salt of vinyl sulfonic acid, styrene sulfonic acid, a styrene sulfonate, an allylsulfonic acid, an allyl sulfonate, methallylsulfonic acid, methallyl sulfonate, vinyl acetate, vinyl stearate, N-vinylimidazol, N-vinylacetamide, N-vinylformamide, N-vinylcaprolactam, N-vinylcarbazole, acrylamide, methacrylamide, N-alkylacrylamide, N-methylolacrylamide, N,N-methylenebisacrylamide, a glycol diacrylate, a glycol dimethacrylate, divinylbenzene, a glycol diallylether, and the like are employed.
Polymerization of VP or copolymerization of VP and other monomers can be carried out according to a solution polymerization in an aqueous solvent. For example, the polymerization can be carried out by adding an aqueous solution of a water-soluble organic peroxide and an aqueous solution of a sulfite to a VP aqueous solution.
As the VP aqueous solution, for example, an aqueous solution having a VP concentration of 10 to 60%, preferably 20 to 50% by weight can be used. When an aqueous solution containing VP and other monomers is employed as the VP aqueous solution, the aqueous solution is 10 to 60% by weight, preferably 20 to 50% by weight in total concentration of VP and other monomers. When the concentration of the VP aqueous solution is low, a low productivity and high cost tend to be caused. When the concentration of the VP solution is high, a trouble in the reaction tends to be caused, because viscosity becomes high with passage of time during polymerization, and stirring becomes difficult.
As the organic peroxide, a water-soluble organic peroxide is preferable because the polymerization system of the present invention is an aqueous system and the sulfite as a reductant in the redox initiator is water-soluble.
As the water-soluble organic peroxide, for example, any hydroperoxides such as tert-butyl hydroperoxide, cumene hydroperoxide, tert-hexyl hydroperoxide and p-menthane hydroperoxide, and a water-soluble peroxyester such as tert-butyl peroxyacetate can be employed. tert-Butyl hydroperoxide is preferable because in case of employing tert-butyl hydroperoxide as an initiator by-products such as tert-butanol can be removed easily by heating at less than 100xc2x0 C., or by decompressing.
A water-soluble organic peroxide is added in an amount of preferably 0.005 to 5%, more preferably 0.02 to 3% by weight based on VP. When a water-soluble organic peroxide is added in a small amount, the polymerization rate tends to decrease causing a low productivity. And when added in a large amount, the peroxide remains as impurities after polymerization, which is not preferable in a product quality, and tends to cause trouble in preparation of a polymer having a relatively high molecular weight.
The water-soluble organic peroxide may be added in a form of a solid or an aqueous solution.
As the sulfite, for example, an ammonium salt of a sulfurous acid comprising sulfurous acid, thiosulfurous acid, hyposulfurous acid and metasulfurous acid and the like, an alkaline metal salt thereof (for example, a sodium salt or a potassium salt thereof), an alkaline earth metal salt thereof (for example, a magnesium salt or a calcium salt thereof) can be employed. Among those mentioned above, ammonium sulfite is more preferable because does not turn into an ash content and can be removed easily for the reason of its high volatility.
The sulfite is added in an amount of preferably 0.005 to 10% by weight, more preferably 0.02 to 7% by weight based on VP. When the sulfite is added in a small amount, a high polymerization ratio becomes difficult to be obtained and non-reacting monomers tend to remain in a large amount. And when added in a large amount, the sulfite or the oxide thereof, i.e. sulfate, tend to remain in products.
The sulfite can be added to a VP aqueous solution, for example, in a form of an aqueous solution.
The mole ratio of the water-soluble organic peroxide and the sulfite is preferably 1:0.5 to 1:20, more preferably 1:1 to 1:10 so that the water-soluble organic peroxide does not remain in products.
The above-mentioned polymerization initiator may be added after or before the temperature of the above-mentioned VP aqueous solution is adjusted to a polymerization temperature.
The above-mentioned polymerization initiator can be added to a reaction solution, for example, collectively or in installments. By adding a polymerization initiator to a reaction solution in installments, for example, a desired and small molecular weight of vinylpyrrolidone polymer can be obtained, and remaining monomers (VP) can be decreased in the resulting vinylpyrrolidone polymer.
When the polymerization initiator is added in installment, by determining the amount of a sulfite added initially so that the mole ratio of the monomer (VP) and the sulfite is 1:0.0004 to 1:0.1, preferable 1:0.005 to 1:0.1, for example, a desired and small molecular weight of a vinylpyrrolidone polymer (K value thereof is 10 to 40) can be obtained. Further, by determining the amount of the sulfite added initially so that the mole ratio of the monomer (VP) and the sulfite is 1:0.0004 to 1:0.08, preferably 1:0.005 to 1:0.08, a desired and small molecular weight of a vinylpyrrolidone polymer (K value thereof is 20 to 40) can be obtained.
The polymerization temperature is preferably 10 to 90xc2x0 C. When the polymerization temperature is low, the polymerization rate and the productivity tend to lower. When the polymerization temperature is high, the radical concentration in the reaction system tends to become high accelerating a termination reaction, and the initiator tends to be used ineffectively and required in a large amount.
The polymerization reaction is almost completed in 0.5 to 10 hours.
According to the present invention, pH control is not necessary during the polymerization in contrast with the case hydrogen peroxide is employed as an initiator. According to the present invention, for example, a vinylpyrrolidone polymer having a K value of 10 to 120 can be obtained.
A K value according to Fikentscher method is a value which represents a molecular weight, and can be evaluated by the means as follows. If the K value is less than 20, a viscosity of the 5% (g/100 ml) aqueous solution is measured. If the K value is at least 20, a viscosity of the 1% (g/100 ml) aqueous solution is measured. The concentration of the sample is calculated based on dry substances thereof. If the K value is at least 20, 1.0 g of the sample is measured precisely, and put into a measuring flask having a capacity of 100 ml. Then, distilled water is added thereto at room temperature to dissolve the sample completely with shaking, and distilled water is added additionally thereto in total 100 ml precisely. Thirty minutes after the resulting sample solution is left to stand in a thermostat (25xc2x10.2xc2x0 C.), a measurement with Ubbelohde viscometer is carried out.
The time required for the sample solution to flow between two of marked lines is measured. The mean is calculated by repeating the measurement several times. Measurement of distilled water is carried out similarly in order to provide a relative viscosity. Two of the resulting flow time are corrected based on a correction value according to Hagenbach-Couette.       K    ⁢          xe2x80x83        ⁢    value    =                                          300            ⁢            C            ⁢                          xe2x80x83                        ⁢            log            ⁢                          xe2x80x83                        ⁢            Z                    +                                    (                              C                +                                  1.5                  ⁢                  C                  ⁢                                      xe2x80x83                                    ⁢                  log                  ⁢                                      xe2x80x83                                    ⁢                  Z                                            )                        2                              +              1.5        ⁢        C        ⁢                  xe2x80x83                ⁢        log        ⁢                  xe2x80x83                ⁢        Z            -      C                      0.15        ⁢        C            +              0.003        ⁢                  C          2                    
In the above formula, Z is a relative viscosity (xcex7 rel) at concentration C, and C is a concentration of a sample (%: g/100 ml).
The relative viscosity xcex7 rel is calculated according to the formula as follows.
xcex7rel=(the flow time of the solution)/(the flow time of water)
According to the present invention, a vinylpyrrolidone polymer which is little colored, gives off a bad smell little, and contains little impurities, especially, the remaining monomer (VP) in vinylpyrrolidone polymers (for example, contains at most 10 ppm) can be obtained. For example, a vinylpyrrolidone polymer which has 10 to 40 of a K value and at most 10 of APHA of a 10% solution and contains at most 10 ppm of remaining monomers (VP) can be obtained.
The resulting vinylpyrrolidone polymer aqueous solution can be converted into solid powders by general means, for example, spray drying, freeze drying, fluidized bed drying, drum drying or belt drying.